Method of separating terpene compounds from gasoline used for extracting rosin from wood



Patented Feb. 7', 1933 I iii/UNITED A VS ATES PATENT. OFFICE ALAN, c. JOHNSTON, or ENVIL, NEW JERSEY, ASSIGNOR 'r'o, HEnctrLEs POWDER -GOM1ANY, F WILMINGTON, DELAWARE, CORPORATION OF DELAWARE mn rnoi) or snrmrineirnnrmvn comrounns rnomsaso nmn USED FOR I ExrnAo'rmG ROSIN mom woon No Drawing Application fiIedfJun'e 19,

My invention relates to a method for separating terpenes from gasoline, "or other petroleum hydrocarbons, used for the extraction of rosin from wood. v

5 As is well known, in the production of'turpentine, pine oil and'rosin by the steamand solvent process, wood-chips are steamed to drive off the oil'of turpentine and most of the pine oil iving turpentine andpine oil which are free r om gasoline or other solvent. The chips are then treatedwith' a solvent, as a low boiling gasoline, for extraction of the rosin. along with such oils as remain 'in'the chips. The gasoline is separated-from the rosin by distillation and there i's'obtained as a by-product a mixture off/terpenes, terpene alcohols, etc.', from which gasoline of the quality generally employed, has not heretofore been separable by fractional distillation,

due to the fact thatthe gasoline and the terterpenes into terpenes of higher boiling range. More particularly, I effect the conversion of the dipentene into its dihydrochloride and the subsequent conversion of the dipentene dihydrochloride formed 40 into terpineol. The gasoline content ofthe mixture is not effected by the treatment and the major portion of the terpenes are ultimately changed into terpineol. Since terpineol boils at about 218 C. as compared 545 with 175 C. at which the dipentene in the 192s. Seria1Il'o.286,713. k I original mixture boils, a temperature which is too close'tO the boiling point of the gasoline to permit of effective separation by fractionation, the fractionation of the converted fer penes'is made comparatively simple. After the conversion of the terpenes the fractionation is accomplished afterfirst steam distill ing thecrude product from an alkalineme diam. I Q In the treatment ofi'themixture of gasoline g and terpene compounds to effect the conversion of the dipentene, I preferlto treat the mixture with hydrogen chloride, which need not be dry, hydrogen bromide, or the like,

and for the alkaline medium, I preferftouse caustic soda, though I may use soda ash (so-' dium carbonate), lime, or the like. 1 .As an example of the carrying out'of my process, I add 10parts of commercial hydro} chlorio acid to 500 parts of gasoline-terpene compound mixture and pass hydrogen chloride'into the mixture. at room temperature until the mixture becomes saturatedl j 'For example, the mixture will be' saturated in aboutfifteen hoursz After the mixture is saturatedI permit it to stand for aboutten hours andthen steam 'distilliit from, forfexample, about 250 parts of 10% aqueoussodiumhydroxide, followed,"if the oil passing 7 over still contains small quantities ofhalogen compounds, by refluxing-for aboutten hoursj with parts of sodium hydroxideinitwo' liters of alcohol fromwhich it issubsequently steam distilled with a yield of about 4Q5Oparts of oil, which may be readily. fractionated; 80 The productmay be refined, forexample,by heating'under pressure,for'example toabout 150 G, with aqueous sodium hydroxide solution for several hours, or by heating with an alcoholic solution of'sodium hydroxide to somewhat lower temperatures, for example, to about C. "Theproduct'm'ay also be refined by heating with about 5 offeither' aniline or sodiumacetate; 9 j As i an example of the effect of the treati pounds from gasoline used in extracting distilling the mixture from an alkaline me ment according to my invention, on the boiling range of the terpene compounds in the mixture, in a typical example, a mixture containing terpenes and gasoline boiling from 5 about 155 C. to about 180 C. was converted into a product having a boiling range from below 165 C. to above 219 C. as shown in p the following table:

Original Treated Per cent C. C. 5 155 165 10 158 177 159 179 162 184 166 191 175 204 180 219 The treated mixture may be readily fractionated and will give airaction consisting largely of terpineol.

1 Having now fullydescribed'my invention,

what I claim and desire to protect by Letters Patentis:

- 1. The method of separating terpene comrosin from wood, from whichturpentine and pine oil have been removed whlch includes I treating a mixture of solvent and terpene compounds with hydrogen chloride, steam dium andfractionating-the mixture. 2. The method of separatingterpene compounds from gasoline, which includes treat- 35 ing a mixture; of gasoline and terpene com- 5. The method ofseparating terpene compounds from gasoline, which includes sat:

urating amixture of'gasoline and terpene compounds with hydrogen chloride, steam distilling the mixture from aqueous sodium hydroxide and fractionating the mixture.

6. The method of separating'terpene com- 7 poundsjfrom gasoline,which includesv saturating a mixture of gasoline and terpene compounds with hydrogen chloride, steam 99;. distilling the mixture from aqueous sodium hydroxide, distilling the terpene, compounds irom alcoholic sodiumfhydroxide and fractionating the distillate. i a A r 7 .The method of separating terpene compounds troll! gfiQline,whiQh includes treating a mixture of gasoline and dipentene with V a reagent to efiect conversion of the dipentene into its dihydrochloride heating the dihydrochloride with an alkali to effect its conversion into terpineol and fractionating the mixture. 8. The method of separating terpene compounds from gasoline, which includes treating a mixture of gasoline and terpene compounds including dipentene with a reagent to effect conversion of the dipentene into its dihydrochloride, steam distilling the mixture the distillate. p

9. The methodof separatingterpene compounds from gasoline, which includes treating a mixture of gasoline, and terpene compounds including dipentene with""a"reagent to effect conversion of the dipentene into its dihydrochloride, steam distilling themixture from caustic soda, heating the distillate'with alcoholic sodium'hydroxide and fractionating the distillate.

10. The method, of separating terpene compounds from gasoline whichincludes treating a mixture of gasoline and a terpene compound with'a hydrogen halide toefl'ect conversion of the terpene compound to a. hydrogen halide terpene addition'product, dis- 'from'an alkaline medium andrfractionating tilling from an alkaline, medium to form tor-,-

pineol and fractionating the distillate.

11. The method of separating dipentene. from gasolinewhich includes treatingfa mixture of gasoline and dipentene with a hydro,

gen halide to effect conversion of'dipentene I.

to a hydrogen halide dipentene addition product, distilling from analkaline, medium to, form terpineol and fractionating the distillate. f V,

a 12. The method of'separa-tingterpene comk pounds other'than turpentine, and pine oil from gasoline, which includes treating a mix-,

ture of gasoline and terpene compounds including dipentene, witha reagent capable of forming a terpene-hydrohalide addition product and treating the reaction mass with an alkaline medium to effect, conversion of the reaction product into terpineol andfrac-f tionating the mixture. V r Intestimony of'whichinvention, I have hereunto set my hand, at Kenvil, 'New J er sey, on this 14th day of June, 1928. g

, AL N JOHNSTON 

